CN108630987B - Gel polymer electrolyte and preparation method and application thereof - Google Patents

Gel polymer electrolyte and preparation method and application thereof Download PDF

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CN108630987B
CN108630987B CN201710158774.0A CN201710158774A CN108630987B CN 108630987 B CN108630987 B CN 108630987B CN 201710158774 A CN201710158774 A CN 201710158774A CN 108630987 B CN108630987 B CN 108630987B
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王玉忠
汪秀丽
夏灵童
黄腾
付腾
何璐
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Sichuan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention provides a gel polymer electrolyte and a preparation method and application thereof. The preparation method of the gel polymer electrolyte comprises the following steps: a metal salt polymerMixing the water-soluble polymer with oxygen capable of generating coordination with metal salt in a structural unit in water, volatilizing a water solvent, generating coordination between metal ions in the metal salt polymer and the oxygen-containing polymer in the structural unit to obtain a porous film, and soaking the porous film in an electrolyte to obtain the gel polymer electrolyte. The preparation process is simple, and the solvent only uses water, so that the preparation method is energy-saving and environment-friendly, and accords with the green development concept. The prepared porous gel polymer electrolyte has the conductivity of 1.39 multiplied by 10 under the room temperature of 25 DEG C‑3S/cm, the electrochemical window reaches 4.5V. The product has good prospect in the field of polymer lithium ion batteries because of environmental protection and low cost.

Description

Gel polymer electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium batteries, particularly belongs to the field of polymer lithium ion batteries, and relates to a gel polymer electrolyte and a preparation method and application thereof.
Background
The lithium ion battery is divided into a liquid lithium ion battery and a polymer lithium ion battery, the liquid lithium ion battery has potential safety hazards such as liquid leakage and explosion, and the polymer lithium ion battery does not have the problems. Meanwhile, the polymer battery is light and thin and has a designable appearance, so that the polymer battery is widely applied to the fields of mobile phones, electric automobiles and the like.
Commonly used polymer matrices are Polymethylmethacrylate (PMMA), polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), and the like. In order to improve the liquid absorption rate of the polymer matrix, the polymer membrane is often prepared into a porous structure, and the conventional method for preparing the porous membrane comprises the following steps: thermally induced phase separation, non-solvent evaporation, electrospinning. The above preparation method is too complicated, or a large amount of organic reagents are used in the process, resulting in cost increase and environmental pollution.
Therefore, there is a need in the art for a porous separator that does not require the use of organic solvents, is simple in preparation process, and is suitable for preparing high-performance electrolytes, and a gel electrolyte prepared from the porous separator and its application in lithium batteries.
Disclosure of Invention
In view of the disadvantages of the prior art, it is an object of the present invention to provide a method for preparing a gel polymer electrolyte, the method comprising the steps of:
(1) mixing a metal salt polymer and a water-soluble polymer containing oxygen capable of generating coordination with metal salt in a structural unit in water, volatilizing a water solvent, and generating coordination between metal ions in the metal salt polymer and the polymer containing oxygen in the structural unit to obtain a porous film;
(2) and (2) soaking the porous film obtained in the step (1) in an electrolyte to obtain the gel polymer electrolyte.
The "metal salt polymer" of the present invention means a polymer containing metal ions, including polyacrylic acid metal salts or ionic liquid metal salts.
The metal salt polymer is a sodium salt polymer or a lithium salt polymer.
The invention finds that the metal salt polymer can play multiple roles in the oxygen-containing water-soluble polymer: metal ions in the polymer can be coordinated with oxygen in the oxygen-containing water-soluble polymer in the structural unit; in addition, the invention also finds that metal ions also participate in ion conduction in the matrix, and directly improves the conductivity performance of the film.
The invention discovers that a porous film and a gel polymer electrolyte with excellent performance can be obtained for a sodium salt polymer or a lithium salt polymer. As shown in the embodiment of the invention, the conductivity of the film obtained by the invention can reach 10-3Scm-1The electrochemical stability window reaches 4.5V. However, as shown in the comparative examples of the present invention, when a sodium salt polymer or a lithium salt polymer, which is not the present invention, is used, the technical effect required in the art cannot be obtained.
Preferably, the structural formula of the metal salt polymer is shown as formula (I) or formula (II):
Figure BDA0001247904560000021
Figure BDA0001247904560000031
wherein R is5Is H atom or methyl; r6Is H atom or methyl; r7Is composed of
Figure BDA0001247904560000032
Figure BDA0001247904560000033
R8Is represented by C1～C3An alkylene group of (a); a represents Li or Na.
Preferably, the structural formula of the oxygen-containing water-soluble polymer is shown as formula (III), formula (IV), formula (V), formula (VI) or formula (VII):
Figure BDA0001247904560000034
in the formula, R1Is a compound of the formula-H,
Figure BDA0001247904560000035
Figure BDA0001247904560000036
in the formula, R2represents-H or-CH2COONa；
Figure BDA0001247904560000041
In the formula, R3is-H or-CH3；
Figure BDA0001247904560000042
In the formula, R4represents-OH, -CONH2Or
Figure BDA0001247904560000043
Figure BDA0001247904560000044
Preferably, the weight ratio of the metal salt polymer to the oxygen-containing water-soluble polymer is 1: 2-20.
Preferably, the weight ratio of the sum of the weight of the metal salt polymer and the oxygen-containing water-soluble polymer to water is 1:10 to 20.
Preferably, the temperature is 40-80 ℃ and the time is 8-16 hours when the water solvent is volatilized.
Preferably, when the film is prepared, the thickness of the film is controlled to be 0.05-0.30 mm.
The electrolyte comprises lithium hexafluorophosphate or lithium bistrifluoromethanesulfonimide.
Preferably, the soaking time is not more than 6 hours.
It is another object of the present invention to provide a gel polymer electrolyte prepared by the above method.
Since the gel polymer electrolyte obtained by the present invention has excellent characteristics, it is still another object of the present invention to provide applications of the above gel polymer electrolyte in the field of lithium batteries.
The invention has the beneficial effects that:
1. the preparation process is simple, and is different from the traditional method for preparing the porous film, and methods such as thermally induced phase separation, electrospinning, non-solvent volatilization and the like are not needed; the preparation method simplifies the preparation process of the porous film, reduces the preparation cost, does not need any organic reagent, and protects the environment;
2. the porous polymer electrolyte prepared by the method has good electrochemical performance, and the ionic conductivity can reach 10 at the maximum at room temperature-3S cm-1The electrochemical stability window reaches 4.5V, meeting the requirements of the polymer lithium battery in practical application.
Drawings
FIG. 1 is a flow diagram of a porous membrane prepared according to the present invention;
FIG. 2 is a scanning electron micrograph of a porous film according to example 3;
FIG. 3 is a scanning electron micrograph of a porous film according to example 7;
FIG. 4 is a plot of the AC impedance spectra at room temperature for examples 1-5;
FIGS. 5 and 6 are the AC impedance spectrum and the Arrhenius fitting curve of example 3 tested at different temperatures;
FIG. 7 is a linear sweep voltammogram of example 5;
FIG. 8 is a plot of the cyclic charge and discharge and their coulombic efficiencies of example 5;
FIG. 9 is a charge-discharge diagram of example 4 with different rates;
FIG. 10 is a film surface topography of comparative example 1;
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Mixing 0.0262g of lithium Polymethacrylate (PMALi) and 0.5238g of hydroxyethyl cellulose (HEC) in 10.45g of water, stirring for 2 hours at room temperature, then pouring 10g of the mixed solution into a glass mold, placing the glass mold in a 60 ℃ oven for 12 hours, taking out the glass mold, cutting the glass mold into a wafer by using a cutter with the radius of 8cm, measuring the thickness of the film by using a micrometer screw, then placing the film in a glove box, immersing the film in a lithium hexafluorophosphate electrolyte for 2 hours to prepare a porous gel polymer electrolyte, and assembling the porous gel polymer electrolyte into a battery test alternating current impedance spectrum with an anode and a cathode both made of stainless steel sheets; assembling a battery test linear sweep voltammetry curve with a stainless steel sheet as a positive electrode and a pure lithium sheet as a negative electrode; the lithium ion battery is assembled into a positive plate with a positive electrode composed of lithium iron phosphate, conductive acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, and a battery with a negative electrode made of pure lithium plates is used for testing the charge and discharge performance of the battery.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 2
Porous films and gel polymer electrolytes were prepared and tested for various properties as in example 1 by mixing 0.0717g of PMALi with 0.4783g of Methylcellulose (MC) in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 3
Porous film and gel polymer electrolytes were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1100g of PMALi with 0.4400g of MC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 4
0.1430g of PMALi was mixed with 0.4070g of hydroxypropyl cellulose (HPC) in 10.45g of water, and a porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 5
A porous membrane and gel polymer electrolyte were prepared and tested for various properties according to the procedure in example 1 by mixing 0.1707g of PMALi with 0.3793g of HPC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1Electrochemically stable windowThe opening is more than 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during cyclic charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 6
0.1265g of sodium polymethacrylate (PMANa) and 0.4235g of MC are mixed in 10.45g of water and stirred for 2 hours at room temperature, then 10g of the mixed solution is poured into a glass mold and placed in an oven at 80 ℃ for 12 hours, the glass mold is taken out and cut into a wafer by a cutter with the radius of 8cm, a spiral micrometer is used for measuring the thickness of the film, then the film is placed in a glove box and immersed in lithium hexafluorophosphate electrolyte for 5 hours to prepare a porous gel polymer electrolyte, and then the porous gel polymer electrolyte is assembled into a battery with the positive electrode and the negative electrode both being stainless steel sheets for testing an alternating current impedance spectrum; assembling a battery test linear sweep voltammetry curve with a stainless steel sheet as a positive electrode and a pure lithium sheet as a negative electrode; the lithium ion battery is assembled into a positive plate with a positive electrode composed of lithium iron phosphate, conductive acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, and a battery with a negative electrode made of pure lithium plates is used for testing the charge and discharge performance of the battery.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 7
A porous film and gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1430g of PMANa with 0.4070g of HPC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 8
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1573g of PMANa with 0.3927g of MC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-4S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, and the coulombic efficiency during the cycle charge-discharge is about 98 percentAnd the battery has good multiplying power charge-discharge recovery performance.
Example 9
Mixing 0.1100g of PMALi and 0.4400g of polyvinyl alcohol (PVA) in 10.45g of water, stirring for 2 hours at room temperature, then pouring 10g of the mixed solution into a glass mold, putting the glass mold in a 40 ℃ oven for 12 hours, taking out the glass mold, cutting the glass mold into a wafer by using a cutter with the radius of 8cm, measuring the thickness of the film by using a spiral micrometer, then putting the film in a glove box, immersing the film in a lithium bis (trifluoromethanesulfonyl imide) electrolyte for 2 hours to prepare a porous gel polymer electrolyte, and assembling the porous gel polymer electrolyte into a battery test alternating current impedance spectrum with a stainless steel sheet as a positive electrode and a negative electrode; assembling a battery test linear sweep voltammetry curve with a stainless steel sheet as a positive electrode and a pure lithium sheet as a negative electrode; the lithium ion battery is assembled into a positive plate with a positive electrode composed of lithium iron phosphate, conductive acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, and a battery with a negative electrode made of pure lithium plates is used for testing the charge and discharge performance of the battery.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 10
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure in example 1 by mixing 0.1265g of PMALi with 0.4235g of PVA in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 11
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1430g of PMALi with 0.4070g of PVA in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 12
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1573g of PMALi with 0.3927g of PVA in 10.45g of water.
Measuring the film conductanceRate of the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V. The battery has good charge-discharge cycle performance, the coulombic efficiency during the cycle charge-discharge is about 98 percent, and the battery multiplying power charge-discharge recovery performance is good.
Example 13
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.2200g of PMALi with 0.8800g of MC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 14
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.2530g of PMALi with 0.8470g of MC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 15
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1100g of PMANa with 0.4400g of PVA in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 16
Mixing 0.1265g of PMANa and 0.4235g of PVA in 10.45g of water, stirring for 2 hours at room temperature, pouring 10g of the mixed solution into a glass mold, placing the glass mold in a 70 ℃ oven for 12 hours, taking out the glass mold, cutting the glass mold into a wafer by using a cutter with the radius of 8cm, measuring the thickness of the film by using a spiral micrometer, placing the film in a glove box, immersing the film in lithium hexafluorophosphate electrolyte for 6 hours to prepare a porous gel polymer electrolyte, and assembling the porous gel polymer electrolyte into a battery with the anode and the cathode both made of stainless steel sheets for testing an alternating current impedance spectrum; assembling a battery test linear sweep voltammetry curve with a stainless steel sheet as a positive electrode and a pure lithium sheet as a negative electrode; the lithium ion battery is assembled into a positive plate with a positive electrode composed of lithium iron phosphate, conductive acetylene black and polyvinylidene fluoride in a mass ratio of 8:1:1, and a battery with a negative electrode made of pure lithium plates is used for testing the charge and discharge performance of the battery.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 17
A porous film and a gel polymer electrolyte were prepared and tested for various properties by mixing 0.2200g of PMANa with 0.8800g of PVA in 10.45g of water according to the procedure of example 1.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 18
A porous film and gel polymer electrolyte were prepared and tested for various properties as in example 1 by mixing 0.1573g of PMALi with 0.3927g of sodium carboxymethylcellulose (CMC) in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 19
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.0916g of PMALi with 0.4584g of CMC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 20
A porous film and a gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1707g of PMALi with 0.3793g of CMC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 21
A porous film and a gel polymer electrolyte were prepared and tested for various properties by mixing 0.0916g of PMANa with 0.4584g of CMC in 10.45g of water according to the procedure of example 1.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 22
Porous films and gel polymer electrolytes were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1100g of PMANa with 0.4400g of CMC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V.
Example 23
0.1265g of PMALi was mixed with 0.4235g of hydroxyethyl cellulose (HEC) in 10.45g of water, and porous film and gel polymer electrolytes were prepared and tested for various properties according to the procedure of example 1.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 24
A porous film and gel polymer electrolyte were prepared and tested for various properties according to the procedure of example 1 by mixing 0.1430g of PMALi with 0.4070g of HEC in 10.45g of water.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 25
A porous film and a gel polymer electrolyte were prepared and tested for various properties by mixing 0.1573g of PMANa with 0.3927g of HEC in 10.45g of water according to the procedure of example 1.
Measured as a film conductivity of the order of magnitude10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Example 26
A porous film and a gel polymer electrolyte were prepared and tested for various properties by mixing 0.1707g of PMANa with 0.3793g of HEC in 10.45g of water according to the procedure of example 1.
The conductivity of the film was measured to be in the order of 10-3S cm-1The electrochemical stability window exceeds 4.5V, the charge-discharge cycle performance of the battery is good, the coulombic efficiency during the cycle charge-discharge is about 98%, and the multiplying power charge-discharge recovery performance of the battery is good.
Comparative example 1
0.143g of potassium Polymethacrylate (PMAK) and 0.407g of MC in 10.45g of water were mixed and stirred at room temperature for 2 hours, then 10g of the mixed solution was poured into a glass mold and placed in an oven at 60 ℃ for 12 hours, as a result of which a film was obtained which was non-porous and, unlike the films of the examples in macroscopic morphology, exhibited significant phase separation.
Comparative example 2
0.143g of the prepared magnesium polymethacrylate (PMAMg) and 0.407gMC g of the prepared magnesium polymethacrylate (PMAMg) were mixed in 10.45g of water, and stirred at room temperature for 2 hours, and it was found that PMAMg in the solution became a gel state in water, and a homogeneous mixed solution could not be obtained, and a film could not be formed.
Comparative example 3
Calcium polymethacrylate (PMAGa) was prepared and found to be insoluble in aqueous solutions and incapable of being blended with oxygen-containing substrates to form films.

Claims (9)

1. A method for preparing a gel polymer electrolyte, comprising the steps of:
(1) mixing a metal salt polymer and a water-soluble polymer containing oxygen capable of generating coordination with metal salt in a structural unit in water, volatilizing a water solvent, and generating coordination between metal ions in the metal salt polymer and the polymer containing oxygen in the structural unit to obtain a porous film;
the structural formula of the metal salt polymer is shown as a formula (I) or a formula (II):
Figure FDA0002362562610000011
wherein R is5Is H atom or methyl; r6Is H atom or methyl; r7Is composed of
Figure FDA0002362562610000012
Figure FDA0002362562610000013
R8Is represented by C1～C3An alkylene group of (a); a represents Li or Na;
the structural formula of the oxygen-containing water-soluble polymer is shown as a formula (III), a formula (IV), a formula (V) or a formula (VI):
Figure FDA0002362562610000014
in the formula, R1Is a compound of the formula-H,
Figure FDA0002362562610000015
Figure FDA0002362562610000016
in the formula, R2represents-H or-CH2COONa；
Figure FDA0002362562610000021
In the formula, R3is-H or-CH3；
Figure FDA0002362562610000022
In the formula, R4represents-OH, -CONH2Or
Figure FDA0002362562610000023
(2) And (2) soaking the porous film obtained in the step (1) in an electrolyte to obtain the gel polymer electrolyte.
2. The preparation method according to claim 1, wherein the weight ratio of the metal salt polymer to the oxygen-containing water-soluble polymer is 1:2 to 20.
3. The method according to claim 2, wherein the weight ratio of the sum of the weight of the metal salt polymer and the oxygen-containing water-soluble polymer to water is 1:10 to 20.
4. The method according to claim 1, wherein the temperature is 40 to 80 ℃ and the time is 8 to 16 hours when the aqueous solvent is volatilized.
5. The method according to claim 1, wherein the film is controlled to have a thickness of 0.05 to 0.30mm when the film is produced.
6. The production method according to claim 1, wherein the electrolyte comprises lithium hexafluorophosphate or lithium bistrifluoromethanesulfonimide.
7. The method of claim 1, wherein the soaking time is no more than 6 hours.
8. A gel polymer electrolyte prepared by the method of any one of claims 1 to 7.
9. Use of the gel polymer electrolyte of claim 8 in the field of lithium batteries.
CN201710158774.0A 2017-03-17 2017-03-17 Gel polymer electrolyte and preparation method and application thereof Active CN108630987B (en)

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